Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/48—Two nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
  • C07D251/64—Condensation products of melamine with aldehydes; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34922—Melamine; Derivatives thereof

Definitions

• This invention relates to the N-1 ,2,2-trihydrocarbyloxyethyl derivatives of certain amino compounds, methods for preparing such denvatives, and compositions containing such derivatives. These derivatives and compositions are particularly suitable for use as crosslinking agents in curable compositions such as coatings, and do not release formaldehyde as a volatile by-product when cured.
• denvatives of ammo compounds such as am ⁇ no-1 ,3,5-t ⁇ az ⁇ nes and glycolu ⁇ ls
• ammo compounds such as am ⁇ no-1 ,3,5-t ⁇ az ⁇ nes and glycolu ⁇ ls
• Certain of these denvatives are useful as crosslinkers in curable compositions which contain resins having active hydrogen groups.
• Non-formaldehyde emitting altemative is the class of isocyanate and carbamate functional 1 ,3,5-triazine crosslinking agents disclosed in commonly owned US4939213, US5084541 , US5288865, EP-A-0604922 (corresponding to United States Application Senal No. 07/998,313, filed December 29, 1992), EP-A-0624577 (corresponding to United States Application Senal No. 08/061 ,905, filed May 14, 1993), EP-A-0649842 (corresponding to United States Application Serial No. 08/138,581 , filed October 15, 1993), WO95/30663 (corresponding to United States Application Serial No.
• Non-formaldehyde emitting alternatives include, for example, the class of lactam substituted 1 ,3,5-triazine crosslinking agents disclosed in commonly owned WO93 10117 (corresponding to United States Application Serial No.
• the present invention also includes a process of preparing such N-1 ,2,2- trihydrocarbyloxyethyl derivative of an amino compound, comprising the steps of reacting (i), (ii) and (iii) under conditions so as to result in a derivative containing, on average, at least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least about 2.0 1 ,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
• the derivatives in accordance with the present invention may comprise substantially a single species of monomeric compound, or may comprise a complex mixture of monomeric and oligomeric compounds.
• the monomeric compounds also form a specific part of the present invention, and can generally be described as compounds comprising an amino core having pendant therefrom at least two 1 ,2,2-trihydrocarbyloxyethyl groups, of the following general formula (I) or (II):
• R 1 is selected from H, a hydrocarbyl and -N(R 2 )(R 3 ); each R 2 is independently selected from H and a hydrocarbyl; each R 3 is independently selected from H, a hydrocarbyl and an R group; each R 4 is independently selected from H and a hydrocarbyl; and each R group is independently a group of the general formula (III)
• each R 5 is independently selected from H and a hydrocarbyl, and each R 6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge; with the proviso that, per molecule, at least two of the R 3 groups are independently an R group, and at least two R 5 groups are independently a hydrocarbyl.
• the aforementioned compounds and derivatives must contain, on average, at least about 2.0 1 ,2,2-trihydrocarbyloxyethyl groups (e.g., a group of the formula (III), wherein R 5 is a hydrocarbyl group) per molecule, which makes these compositions particularly suitable for use as crosslinking agents in a variety of end applications.
• the present invention consequently, also relates to curable compositions comprising (a) a crosslinker component comprising the compounds and/or compositions in accordance with the present invention, and (b) a resin component comprising a compound containing at least two groups capable of reacting with the 1 ,2,2- trihydrocarbyloxyethyl groups of (a).
• the derivatives in accordance with the present invention are primarily reactive via the activated ether of the 1 ,2,2-trihydrocarbyloxyethyl group (e.g., tl.e hydrocarbyioxy in the 1 position). It has been su ⁇ risingly found that, without the presence of sufficient such activated ether functionality, good curing results cannot be obtained. Groups capable of reacting with 1 ,2,2-trihydrocarbyloxyethyl groups are, therefore, groups capable of reacting with activated ether groups within the meaning of the present invention, which are the same types of groups that are reactive with the alkoxymethyl and methylol functionality of traditional amine-formaldehyde crosslinkers.
• a particularly advantageous such use of the curable compositions of the present invention is in the form of a coating composition.
• the present invention also relates to curable coating compositions, methods for coating substrates as well as the substrates coated therewith, crosslinked films or objects derived from the curable composition ⁇ , and various other end uses thereof.
• the compounds and compositions of the present invention are prepared without using formaldehyde and therefore are formaldehyde-free.
• Curable compositions employing these compounds and compositions as crosslinkers can also be formulated as formaldehyde free systems.
• Other advantages include rapid cure, adaptability to waterborne coatings systems, and ability to produce fully cured coatings which have excellent appearance and film and resistance properties.
• an amino compound having at least two NH groups, selected from the group consisting of amino- 1 ,3,5-triazines, glycolurils and oligomers thereof, (ii) a 2,2-dihydrocarbyloxy ethanal, and (iii)
• hydrocarbyl within the context of the present invention, is a group which contains carbon and hydrogen atoms and includes, for example, alkyl, aryl, aralkyl, alkenyl and substituted derivatives thereof.
• amino compounds are amino-1 ,3,5-triazines and glycolurils of the general formulas (IV) and (V):
• R 1 is selected from H, a hydrocarbyl and -N(R 7 ) 2
• each R 7 is independently selected from H and a hydrocarbyl, with the proviso that at least two groups R 7 are H, and preferably that all R 7 groups are H
• each R 4 is independently selected from H and a hydrocarbyl, and preferably that all R 4 groups are H.
• R 7 groups are H
• R 1 is selected from H and a hydrocarbyl; more preferably H, an alky! of 1 to 20 carbons atoms, an aryl of 6 to 20 carbon atoms and an aralkyl of 7 to 20 carbon atoms; and particularly a phenyl group (benzoguanamine), a methyl group (acetoguanamine) and a cyclohexyl group (cyclohexylcarboguanamine).
• the preferred amino compound of the general formula (V) (wherein all R 4 and R 7 groups are H) is glycoluril.
• each R 6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge.
• Such 2,2-dihydrocarbyloxy ethanals and methods for their preparation are disclosed in US4835320, which is inco ⁇ orated herein by reference for all pu ⁇ oses as if fully set forth.
• Preferred are those wherein each R 6 is independently an alkyl of 1 to 8 carbon atoms or an alkenyl of 1 to 8 carbon atoms, as well as those wherein both R 6 groups together form an alkylene bridge of 1 to 8 carbon atoms.
• Particularly preferred are those wherein each R 6 is independently an alkyl of 1 to 8 carbon atoms, and those wherein both R 6 groups together form an alkylene bridge of 1 to 4 carbon atoms.
• Specifically preferred examples include 2,2-dimethoxy ethanal, 2,2-diethoxy ethanal, 2- methoxy-2-ethoxy ethanal, 2,2-dipropoxy ethanal, 2,2-dibutoxy ethanal, 2,2-dipentoxy ethanal, 2,2-dihexoxy ethanal, 2,2-dicyclohexoxy ethanal, 2,2-ethylenedioxy ethanal and 2,2-propylenedioxy ethanal.
• DME 2,2-dimethoxy ethanal
• hydrocarbylol are hydroxy group-containing compounds having from 1 to 20 carbon atoms such as, for example, alkylols, alkenols, phenols and alkoxyalkylols.
• alkylols such as, for example, alkylols, alkenols, phenols and alkoxyalkylols.
• alkylols such as, for example, alkylols, alkenols, phenols and alkoxyalkylols.
• alkylols 1, 2-butanols, 1,8-diols.
• the derivatives in accordance with the present invention contain, on average, at least about 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least about 2.0 1 ,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
• the guanamine derivatives preferably contain on average from about 1.5 to about 2.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of guanamine.
• a specific preferred embodiment is a substantially monomeric guanamine derivative which contains about 2.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of guanamine.
• R 1 is selected from H and a hydrocarbyl, preferably selected from H, an alkyl of 1 to 20 carbons atoms, an aryl of 6 to 20 carbon atoms and an aralkyl of 7 to 20 carbon atoms, and especially selected from a phenyl group, a methyl group and a cyclohexyl group
• each R 2 is selected from H and a hydrocarbyl, and preferably H
• each R 3 is a group of the formula (III)
• each R 5 is independently a hydrocarbyl, preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls and alkoxyalkylyls, and especially independently an alkyl of 1 to 8 carbon atoms
• each R 6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge, preferably independently selected from an alkyl
• the melamine derivatives preferably contain on average from about 2.0 to about 3.0 moles and, more preferably, from about 2.3 to about 3.0 moles, of combined 2,2- dihydrocarbyloxy ethanal per mole of melamine.
• a specific preferred embodiment is a substantially monomeric melamine derivative which contains about 3.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of melamine.
• R 1 is -N(R )(R 3 ); each R 2 is selected from H and a hydrocarbyl, and preferably H; each R 3 is a group of the formula (III); at least two of the R 6 groups, and preferably each of the R 5 groups, are independently a hydrocarbyl, preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls and alkoxyalkylyls, and especially independently an alkyl of 1 to 8 carbon atoms; and each R 6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge, preferably independently selected from an alkyl of 1 to 8 carbon atoms and an alkenyl of 1 to 8 carbon atoms, or together form an alkylene bridge of 1 to 8 carbon atoms, and especially independently an alkyl of 1 to 8 carbon atoms, or together form an alkyl
• a specific preferred embodiment is a substantially monomeric glycoluril derivative which contains about 4.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of glycoluril.
• each R 3 is a group of the formula (III); each R 4 is independently selected from H and a hydrocarbyl, and preferably H; at least two of the R s groups, preferably at least three of the R 5 groups, and especially each of the R 5 groups, are independently a hydrocarbyl, preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls and alkoxyalkylyls, and especially independently an alkyl of 1 to 8 carbon atoms; and each R 6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge, preferably independently selected from an alkyl of 1 to 8 carbon atoms and an alkenyl of 1 to 8 carbon atoms, or together form an alkylene bridge of 1 to 8 carbon atoms, and especially independently an alkyl of 1 to 8 carbon atoms, or together form an alkyl
• N-1,2,2-trihydrocarbyloxyethyl derivatives described above may be prepared in accordance with the present invention by reacting (i), (ii) and (iii) under conditions sufficient to produce a derivative having, on average, at least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least about 2.0 1 ,2,2- trihydrocarbyloxyethyl groups per molecule of derivative.
• (i) and (ii) are contacted in a first step in the presence of a basic catalyst to produce a 1-hydroxy-2,2- dihydrocarbyloxyethyl derivative intermediate, which in a subsequent step is reacted with (iii) (e.g., alkylated) under acidic conditions (preferably in the presence of an acid catalyst).
• the first step is typically conducted in an aqueous medium, at temperatures generally ranging from ambient to about 120°C.
• the intermediate is isolated and added to an organic solvent for the second step.
• an excess of the hydrocarbylol (iii) may be used as the organic solvent.
• reaction of the intermediate from the first step and (iii) is typically carried out under conditions and with acid catalysts similar to those involved in an alkylating step for traditional amine-formaldehyde resins, which conditions and catalysts are well-known to those of ordinary skill in the art.
• the curable compositions in accordance with the present invention comprise:
• crosslinker component comprising an N-1 ,2,2-trihydrocarbyloxyethyl derivative as described above, and (b) a resin component comprising a compound containing at least two groups capable of reacting with the 1 ,2,2-trihydrocarbyloxyethyl groups of (a).
• the crosslinker component may optionally comprise a variety of additional ingredients.
• the crosslinker component may optionally contain other crosslinking agents, referred to herein as "co-crosslinkers," which include, particularly, active-hydrogen and epoxy reactive crosslinking agents such as, for example, traditional amine-formaldehyde resins, blocked and/or unblocked polyfunctional isocyanates, and isocyanate and carbamate functional 1 ,3,5-triazine carbamate crosslinkers.
• co-crosslinkers include, particularly, active-hydrogen and epoxy reactive crosslinking agents such as, for example, traditional amine-formaldehyde resins, blocked and/or unblocked polyfunctional isocyanates, and isocyanate and carbamate functional 1 ,3,5-triazine carbamate crosslinkers.
• suitable amine-formaldehyde resins may be mentioned the partially or substantially fully methylolated, partially or substantially fully etherified amino compounds based on melamine, guanamines, glycolurils and urea.
• such amine- formaldehyde resins are well known to those of ordinary skill in the art (see, for example, the numerous previously inco ⁇ orated references) and are generally available commercially. Most commonly, they include melamines, guanamines such as benzo-, aceto- and cyclohexylcarbo-guanamines, glycolurils and ureas, as well as the at least partially N-alkylolated and N-alkoxyalkylated derivatives thereof, and oligomers thereof.
• melamines such as benzo-, aceto- and cyclohexylcarbo-guanamines, glycolurils and ureas
• the at least partially N-alkylolated and N-alkoxyalkylated derivatives thereof and oligomers thereof.
• commercially available amino resins of the type described above may be mentioned those sold under the trademarks CYMEL® and BEETLE® of Cytec Industries, Inc. (West Paterson, New
• Polyisocyanate crosslinking agents including blocked forms thereof, are generally well known in the art and have been extensively used in coating compositions in a monomeric, oligomeric and/or polymeric form, and preferably contain at least two reactive isocyanate groups.
• hexamethylene diisocyanate 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4- trimethylhexamethylene diisocyanate; meta- ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylenediisocyanate (commercially available under the trade designation m-TMXDI ® aliphatic isocyanate from Cytec Industries Inc., West Paterson, New Jersey); para- ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethylxylylenediisocyanate (available under the trade designation p-TMXDI ® aliphatic isocyanate from Cytec Industries Inc., West Paterson, New Jersey); 1- isocyanato-3,3,5-trimethyl
• uretdione derivatives of various diisocyanates including, for example, hexamethylene diisocyanate and IPDI
• isocyanurate derivatives of various diisocyanates including, for example, hexamethylene diisocyanate (commercially available under the trade designation Desmodur® N 3390 of Miles Inc., Pittsburgh, Pennsylvania) and IPDI (commercially available under the trade designation IPDI ® T
• isocyanate and carbamate functional 1 ,3,5-triazine carbamate crosslinkers may be mentioned those having on average at least two isocyanate and/or carbamate groups attached to one or more 1 ,3,5-triazine cores.
• these 1 ,3,5- triazine compounds are also well known to those of ordinary skill in the art, as exemplified by the numerous references previously inco ⁇ orated above.
• Suitable for use as the resin component are compounds containing at least two groups capable of reacting with the 1 ,2,2-trihydrocarbyloxyethyl groups of (a) such as, for example, active hydrogen and/or epoxy groups, which are generally the same types of materials suitable for use in traditional amine-formaldehyde resin crosslinked systems.
• Preferred are the polyfunctional active hydrogen group containing compound.
• Active hydrogen-containing functionality refers to functional groups which contain active hydrogens as is generally well-known to those of ordinary skill in the art and includes, most commonly, hydroxyl, carboxyl and amino groups. When utilized herein, hydroxyl is preferred.
• Suitable such polyfunctional hydroxy group containing materials are again generally well known to those skilled in the art, and contain at least two and preferably more than two hydroxy groups. Reference may be had to previously inco ⁇ orated US4939213, US5084541 , US5288865, EP-A-0604922 (corresponding to United States Application Serial No. 07/998,313, filed December 29, 1992), EP-A-0624577
• acrylic or polyester backbone resins examples include acrylic resins which may be obtained by the copolymerization of acrylic or methacrylic esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or methacrylate, optionally with simultaneous use of additional vinyl compounds such as, for example, styrene.
• acrylic resins which may be obtained by the copolymerization of acrylic or methacrylic esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or methacrylate, optionally with simultaneous use of additional vinyl compounds such as, for example, styrene.
• polyfunctional hydroxy group containing materials also include polyester resins which may be obtained, for example, by the reaction of polycarboxylic acids with excess quantities of polyhydric alcohols.
• polyfunctional hydroxy group containing resins include polyurethane prepolymers, alkyds, as well as hydroxy group containing epoxy prepolymers such as those resulting from the reaction of a polyfunctional epoxy group containing compound with an amine or with a polyfunctional carboxylic acid derivative.
• such resins may have pendent or terminal hydroxyl functionalities and preferably have the following characteristics: weight average molecular weights (Mw) of from about 750 to about 7000, and more preferably from about 2000 to about 5000; and hydroxyl numbers of from about 20 to about 120 mg KOH/g resin.
• Mw weight average molecular weights
• polyfunctional hydroxy group containing materials having thereon aqueous dispersion promoting groups such as carboxylic or sulfonic functionalities and higher molecular weights are generally usable, such as disclosed in previously inco ⁇ orated WO96/15185, as well as GB1530022, EP-A-0568134, EP-A- 0663413, US5075370 and US5342878, al!
• Solid polyfunctional hydroxy group containing materials are suitable for use in powder coatings.
• liquid polyfunctional hydroxy group containing materials are preferred.
• solid polyfunctional hydroxy group containing materials may be used in cases when the solids are soluble in the solvent used in a particular formulation.
• Specific suitable hydroxyl functional resins will be readily recognized by those of ordinary skill in the art depending upon the desired end use.
• polyfunctional hydroxy group containing materials include JONCRYL ® 500 acrylic resin, a product of S.C.Johnson & Sons, Racine, Wl; ACRYLOID ® AT-400 acrylic resin, a product of Rohm & Haas, Philadelphia, PA; CYPLEX ® 1531 polyester resin, a product of Cytec Industries, West Paterson, NJ;
• CARGILL 3000 and 5776 polyester resins products of Cargill, Minneapolis, MN; TONE ® polyester resin, a product of Union Carbide, Danbury, CT; K-FLEX ® XM-2302 and XM- 2306 resins, products of King Industries, Norwalk, CT; CHEMPOL ® 1 1-1369 resin, a product of Cook Composites and Polymers, Port Washington, Wl; JONCRYL ® 540 acrylic emulsion polymer, a product of S.C.Johnson & Sons, Racine, Wl; RHOPLEX ® AC-1024 acrylic emulsion resin, a product of Rohm & Haas, Philadelphia, PA; XC ® 4005 water reducible acrylic resin, a product of Cytec Industries, West Paterson, NJ; CRYLCOAT* 3494 solid hydroxy terminated polyester resin, a product of UCB CHEMICALS USA, Smyrna, GA; RUCOTE ® 101 polyester resin, a product of
• the curable compositions of the present invention may optionally comprise a variety of additional ingredients normal for any particularly chosen end use.
• Suitable cure catalysts include those typically suited for use in traditional amine-formaldehyde crosslinked systems, such as protic acid catalysts and Lewis acid catalysts.
• protic acid catalysts may be mentioned sulfonic acids such as p-toluene sulfonic acid or dodecyl benzene sulfonic acid.
• Other examples include aryl and alkyl acid-phosphates and pyrophosphates, carboxylic acids, sulfonimides, mineral acids, and the like.
• Latent acidic catalysts such as amine-blocked p-toluene sulfonic acid or amine-blocked dodecyl benzene sulfonic acid, are included within the meaning of protic acid catalysts.
• the Lewis acid catalysts may be mentioned compounds of aluminum, boron, magnesium, antimony and tin.
• the use of cure catalysts are optional in the present systems and, when utilized, are generally added in amounts ranging from about 0.001 wt % to about 6.0 wt %, and preferably up to about 2.0 wt %, based on the combined weight of the resin and crosslinker components (total resin solids).
• the present curable compositions may also contain a solvent of the type typically found in coatings applications including, for example, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like.
• the curable compositions may contain, in addition to water, a co-solvent and an aqueous dispersion promoting material such as ethylhexanol, Texanol ® (a C8-hydroxyalkyl ester of methylpropionic acid commercially available from Eastman Chemical Company), surfactants and other related materials.
• Other optional ingredients may be additionally used depending on the particular application.
• auxiliaries and additives typically utilized in the coatings industry including, for example, foam inhibitors, levelling aids, pigments, dispersants such as pigment dispersing aids, dyes, UV absorbers, heat stabilizers, other stabilizing additives such as antioxidants, and the like.
• foam inhibitors levelling aids
• pigments dispersants
• dispersants such as pigment dispersing aids
• dyes dyes
• UV absorbers heat stabilizers
• other stabilizing additives such as antioxidants, and the like.
• Other optional ingredients have been exemplified in the many previously inco ⁇ orated references, and reference may be had thereto for further details.
• the curable compositions of the present invention are suitable for numerous uses including, for example, as coatings and adhesives, in decorative laminated boards, in the formation of crosslinked molded articles such as engineering composites, for textile and paper treatment, and in any other field in which traditional amine- formaldehyde resins are suitable for use.
• the curable compositions may be prepared by admixing the various components via methods and in relative amounts which are recognizable by those of ordinary skill in the art in the relevant field depending upon the particular end use chosen.
• the resin component and the crosslinker component should preferably be admixed in an equivalents ratio (equivalents of reactive functionality) of from about 0.5:1 to about 2:1 , and more preferably from about 0.8:1 to about 1.2:1.
• curable compositions in accordance with the present invention is in the coatings field.
• Any conventional type of coating may be prepared using the curable compositions described herein, including organic solvent based liquid coatings, waterborne coatings, powder coatings and high temperature coil coatings.
• the weight amounts of the various reactive components will be dependent upon factors including, for example, the particular materials chosen, the presence of other reactive species as well as the desired end use. Based upon these variables and others, those of ordinary skill in the art should be able to adjust the composition of the coatings (including the relative amounts of the components) to achieve the desired effect.
• Organic solvent based liquid coatings in accordance with the present invention may be prepared via conventional means by adding into a commonly used organic coatings solvent the components of the curable composition and the optional ingredients, if present, in any convenient order.
• the systems are formulated to produce a solids content level suitable for convenient application with minimal material loss, preferably at a solids content level in the range of from about 20 weight percent to about 85 weight percent, and more preferably at a solids content level in the range of from about 45 weight percent to about 80 weight percent, depending on the method of application chosen.
• Waterborne coating compositions in accordance with the present invention may be prepared by combining the components of the coating in any particular order, but it is preferred to do so by preparing a dispersible composition by substantially homogeneously mixing the coating components with a surface active material (which may be an inherent property of the resin component), then dispersing the dispersible composition in an aqueous medium, which may comprise solely water or may contain other components such as minor amounts of water-miscible co-solvents to ease dispersion or adjust viscosity.
• the waterborne coating compositions may be formulated to various solids contents, generally ranging from about 20% to about 75% by weight solids, but preferably in the range of from about 30% to about 55% by weight solids, depending on the method of application chccon.
• Powder coating compositions in accordance with the present invention may be prepared by any well-known method, for example, by dry mixing the components in a mixer or blender followed by compounding in an extruder and granulating, grinding and then screening to obtain a powder of suitable mesh size for powder coating.
• compositions containing solid crosslinker and backbone resin components are preferred. Altematively, some or all of the components may be dissolved in a solvent such as methylene chloride and spray dned by well known techniques.
• the present coating compositions are utilized by applying the coating to a substrate then curing the so-applied coating to form crosslinked films.
• Liquid coatings may be applied, for example, by dipping, spraying, padding, brushing, flowcoating, electrocoating or electrostatic spraying. After application, the liquid carrier (e.g., organic solvent and/or water) is generally allowed to partially evaporate to produce a uniform coating on the substrate.
• Powder coatings may be applied, for example, by means such as a powder gun, electrostatic deposition or deposition from a fiuidized bed. After deposition, the powder is typically heated usually to a temperature sufficient to cause the particles to soften, melt, flow and begin to cure.
• Full curing of the present coating compositions requires elevated temperatures generally in the range of from about 25°C to about 450°C depending on the components as well as the end use application.
• the cure temperature is typically in the range of from about 80°C to about 160°C.
• the cure temperature is typically in the range of from about 110°C to about 230°C, preferably from about 150°C to about 220°C, and most preferably from about 170°C to about 200°C.
• the cure temperature is typically in the range of from about 250°C to about 450°C.
• Cure time preferably is in the in the range of from about 1 second to about 30 minutes but may vary depending on the temperature chosen for cure.
• a fully cured coil coating may be obtained by either curing at 260°C for 1 minute or by curing at 417°C for 20 seconds.
• Typical cure times for liquid and powder coatings are in the in the range of from about 5 minutes to about 30 minutes.
• the coating compositions of this invention may be formulated for use in numerous areas such as original equipment manufacturing (OEM) including automotive coatings, general industrial coatings including industrial maintenance coatings, architectural coatings, can coatings and the like. They are usable as coatings for wire, appliances, automotive parts, furniture, pipes, machinery, and the like.
• OEM original equipment manufacturing
• the present systems can be used as 1 K coatings in applications such as automotive finishes, powder coatings, coil coatings including base coats and top coats. Suitable surfaces include metals such as steel and aluminum, plastics, wood, and glass.
• Xylenes (ACS reagent), p-toluenesulfonic acid (practical), methanol (100 %, ACS reagent) and methylene chloride (ACS reagent) were obtained from J. T. Baker Chem. Co, Phillipsburg, N.J. Buffer solutions (Baxter calibrating buffer, pH 4, 7 and 10) were obtained from Baxter Diagnostics, Inc., Deerfield, IL. Water used was deionized water. All amounts are expressed as parts by weight, unless otherwise stated.
• the DME utilized was pu ⁇ fied by distilling a 43 % solution of DME in methyl tertiary butyl ether (MTBE) (552 g total) under reduced pressure (72 mm/Hg) The fraction boiling at 50-60°C was collected as a colorless liquid (174 g, yield 73%).
• MTBE methyl tertiary butyl ether
• Example 1 the 3 C NMR was consistent with the composition represented by the formula (Melamine)(DME) 3 (Me) 3 .
• EXAMPLE 4 Melamine (20 g, 0.16 moles), methanol (77 g, 2.4 moles), DME (freshly purified, 50 g, 0.48 moles) and concentrated nitric acid (2 g, 0.032 moles) were placed in a 500 ml reaction flask under a nitrogen atmosphere and stirred at reflux for 24 hr. The reaction mixture was then cooled to room temperature and neutralized to pH 7 (buffer pH 7) by 50 % NaOH. The solution was filtered to give a colorless solution. 13 C NMR of the product indicated an average composition of (Melamine)(DME) 23 (Me), 6 .
• EXAMPLE 6 Melamine (45.4 g, 0.36 moles), n-butanol (400 g, 5.41 moles), DME (freshly purified, 150 g, 1.44 moles) and p-toluenesulfonic acid (0.93 g, 0.005 moles) were placed in an one litter reaction flask under a nitrogen atmosphere and stirred at 70-80°C for 24 hr. The solvent was removed under reduced pressure using a rotary evaporator (6 mm/Hg, 50°C). The residue was dissolved in methylene chloride (400 ml) and washed with water (2 x 300 ml), NaHCO 3 (2 x 200 ml) and water (2 x 300 ml).
• Coatings A-J were prepared by admixing the components with enough additional solvent to adjust the solids level to the percentage, as listed in Tables l-X below. Films derived from Coatings A-J were compared to films derived from comparative coatings (Comparative Coatings A-J) using a conventional-type methylated melamine- formaldehyde resin as crosslinker. The physical and resistance properties of the coatings and the comparatives are also provided in Tables l-X. These results show that curable systems based on the present compounds and compositions can be formulated to produce results comparable to those obtained from more conventional systems crosslinked with traditional amino-fo ⁇ maldehyde crosslinkers.
• Catalyst (Cycat ® 296-9) (6) 1.0 Wt % 1 .0 Wt %
• KHN 25 10.5 15.3 MEK 200+/200+ 200+/200+
• Catalyst (CYCAT ® 296-9) 1.0 Wt % 1.0 Wt %
• Coating K was prepared by admixing the components with enough additional solvent to adjust the solids level to the percentage, as listed in Table XI below. A film derived from Coating K was compared to a film derived from a comparative coating
• Appearance Good Poor EXAMPLES 9 AND 10 Waterborne Coatings L and M were prepared by admixing the components as listed in Tables XII-XIII below. Films derived from Waterborne Coatings L and M were compared to films derived from comparative coatings (Comparative Coatings L and M) using a conventional-type methylated melamine-formaldehyde resin as crosslinker. The physical and resistance properties of the coatings and the comparatives are also provided in Tables XII-XIII. These results show that curable waterborne systems based on the present compounds and compositions can be formulated to produce results comparable to those obtained from more conventional systems crosslinked with traditional amino-formaldehyde crosslinkers.
• Rhoplex ® AC1024 Polyfunctional Material
• Rhoplex ® AC1024 Rhoplex ® AC1024

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